Water insoluble monoazo dyestuffs



United States Patent WATER INSOLUBLE MONOAZO DYESTUFFS WinfriedKruckenberg, Leverkusen-Bayerwerk, Germany, assignor to FarbenfabrikenBayer Aktiengesellschaft, Leverkusen, Germany, a corporation of GermanyNo Drawing. Application October 25, 1955 Serial No. 542,762

Claims priority, application Germany November 20, 1954 7 Claims. (Cl.260-155) The present invention relates to new water insoluble monoazodyestufls and a process of making the same; more particularly, itrelates to monoazo dyestutfs corresponding to the formula:

wherein Ar means an aromatic radical of the benzene or naphthaleneseries, R stands for hydrogen, alkyl, hydroxy alkyl or acylated hydroxyalkyl, the hydroxy alkyl may be attached to Ar with ring-formation, andR stands for hydrogen or an acyl radical, the azo bridge and the groupstanding in Ar in p-position to each other, and wherein the benzenenucleus, bearing the CN-group, is further substituted by alkyl and/orhalogen and/ or cyano.

It is an object of the present invention to provide a new process forthe manufacture of water insoluble monoazo dyestuffs.

It is a further object of the present invention to provide new waterinsoluble azo dyestufis of good fastness properties.

In my copending application Ser. No. 432,313, filed May 5, 1954, waterinsoluble monoazo dyestulfs are described which can be obtained bycoupling diazotized cyano anilines which are further substituted in thebenzene nucleus by alkyl and/or halogen and/or cyano with aromaticamines of the benzene series being capable of coupling in p-position tothe amino group, one of the hydrogen atoms of the amino group beingreplaced by a hydroxy alkyl group and the other hydrogen atom by analkyl or hydroxy alkyl group and the diazo and coupling components beingfree from carboxylic and sulfonic acid groups.

In accordance with the present invention I have now found that valuablewater insoluble monoazo dyestufis are obtainable by coupling diazotizedcyano anilines which are further substituted in the benzene nucleus byalkyl and/or halogen and/or cyano with aromatic amines of the benzene ornaphthalenes series being capable of coupling in p-position to the aminogroup, wherein one of the hydrogen atoms of the amino group may bereplaced by alkyl or hydroxy alkyl; and the hydroxy alkyl may beattached to the nucleus carbon atom in o-position with ring-formation.and coupling components, are free from sulfonic and carboxylic acidgroups. The coupling components are those frequently used in themanufacture of water insoluble azo dyestuifs particularly suited for.dyeing cellulose acetate fibres.

The dyestuffs thus obtained may be subsequently acylated; if a N-hydroxyalkyl group is present in the coupling component, it can be esterifiedtoo.

The components, e.g. diazo The new water insoluble monoazo dyestuffsyield clear orange to blue dyeings of good fastness to light and washingon polyamide and cellulose acetate fibres. The new dyestuffs aredistinguished by the property to yield equal or almost equal shades ofparticular clearness and of equal or almost equal fastness to light onboth types of fibres. By this quality they excel the known comparablewater insoluble monoazo dyestuffs which are substituted in the diazocomponent by a nitro group.

The present invention is illustrated by the following examples however,without being restricted thereto; the parts being by weight:

Example 1 15.3 parts of 1-amino-2-cyano-5-chlorobenzene are dissolved in50 cc. of concentrated hydrochloric acid, upon which 35 parts of a 20percent sodium nitrite solution are run in with good stirring andcooling. After diazotization is complete, the solution is filtered,partly neutralized (Congo-red paper shall show a violet stain) withdilute caustic soda solution and combined with a solution of 15.1 partsof 1-N-hydroxyethylamino-3-methyl benzene in dilute hydrochloric acid.Coupling is made complete by adding sodium acetate, whereby the azodyestuft separates as a red powder. The dyestuif is filtered off andwashed neutral. When dry, it forms a light red powder which dissolves inorganic solvents with an orange color. The dyestuti corresponds to theformula:

and dyes, after being finely dispersed by means of suitable agents,acetate rayon and polyamide fibres clear orange shades.

Example 2 CHg.CHg-0.0CCH

It dyes, after being finely dispersed by means of suitable agents,acetate rayon and polyamide fibres in clear orange shades.

Example 3 15.3 parts of 1-amino-3-chloro-4-cyanobenzene are diazotizedwith 50 parts of concentrated hydrochloric acid and 35 parts of a 20percent sodium nitrite solution and coupled with 12.8 parts of1-amino-2,5-dimethylbenzene in the manner described in Example 1. Thedyestuft' obtained corresponds to the formula:

It dyes, after being finely dispersed by means of suited agents, acetaterayon and polyamide fibres in clear orange shades.

asses-so Example 4 HO N H is filtered with suction and dried. Itrepresents a black powder which dyes acetate rayon and polyamide fibresin clear reddish-blue shades.

Example 14.3 parts of 1-amino-2,4-dicyano-benzene are dissolveddispersed by means of suitable agents, it dyes acetate rayon andpolyamide fibres in clear bluish-red shades.

Example 6 A dyestuff is obtained by the manner described in Example 5from 15.7 parts diazotized l-amino-2-methyl-4,6- dicyanobenzene and 15.1parts of 1-N-hyd1'oxy-ethyl-3- methylbenzene. The dry black-red powderis heated to the boil with an excess of acetic anhydride for about 30minutes. Then the mixture of acetic acid and acetic anhydride isdistilled oil as much as possible in vacuum. The residue is finelyground with Water, filtered with suction and dried. The dyestuffobtained, corresponding to the following formula:

CH5.CHg-0.0CCH3 is a black red powder which dyes, after being finelydispersed by means of suitable agents, acetate rayon and polyamidefibres in clear bluish-red shades.

in 460 parts of concentrated sulfonic acid at 0l5 C. and Example 7diazotized with 170 parts of nitrosylsulfuric acid (42 parts 14 3 partsof 1 amino 2 4 dicyano benzene are diazm of nitrite in 100 cc.) withgood stirring and coolingtized as described in Example 5 The diazo saltsolution After about 3 hours the mixture is added to 3000 parts of isadded to an aqueous Solution'of 25 2 parts of Py tetra ice, a slightexcess of nitrite removed by adding amido hydro 3 6, dihydroxy 7 8zxbenzoqliinolinel The ig g l a i s gg g xgg g g iz' sg' :1 2; ture ispartly neutralized (Congo red paper shall show a l-l l -sydi gigethylamino-3-methylbenzene the rnb r ture is violet Stain) wi diluteciustic Soda and coupling is partly neutralized (Congo red paper shallshow violet addmog mi The dyesmfi obstain) with dilute caustic soda andcoupling is completed ne correspon s o 6 0m by adding sodium acetate.The dyestuff obtained corre- E2 sponding to the formula: N=N CH-OH N=NNH-CH -CH -OH NC CN HO g CN CN H3 40 It represents a black powder whichdyes acetate rayon and polyamide fibres in clear strongly greenish-blueshades.

Diazo component Shade on- Azo component acetate rayon polyamide fibrel-arnino-3-chloro-4-cyano-benzene D0 l-amino-2-cyano-5-chlorobenzene DoD 1-amlno-2,4-dicyanobenzene D o 1-emino-2,4-dicyano-3,6-dimethylbenzenel-N-hydroxyethylamino 3 methylstrongly reddish scarlet.

benzene. orange. l-N-hydroxyethylamino 3 methyl? do strongly reddishbenzene dyestufli subsequently acetylated orange.

l-amino-3-methylbenzene yellowish 0range.. yellowish orange. 1 Nethylamino-B-methylbenzeneorange orange.

1 amino 2,5-dirnethylbenzene. do D0. N-hydroxyethylaminobenzene.yellowishorange yellowish orange. 1 N -hydroxyethylamino 3methylstrongly reddish strongly reddish benzene. 1 N bntylamino 3methylbenzene 1 amino 2,5 dimethylbenzene- 1 N hydroxyethylamino 3 methbenzene dyestufi subsequently acetorange.

orange. yellowish orange. orange.

ylated. pytrahydro 3,6 dihydroxy 7,8,1, reddish blue reddish blue.

2 benzoqnlnoline. 1 amino 6 hydroxynaphthalene. bluish red bluish red.1-amino-7-hydroxynaphthalene do bluislh Bordeaux rei-amino-zmethyl-5ethoxybenzene orange orange. py tetrahydro 3.6dihydroxyblue greenish blue.

7,8,1,2-benzoquinoline. 1 N hydroxyethylamino 3 methylred bluish red.

benzene dyestnfi subsequently acetylated. 1 N ethylamino 3methylbenzene-. -do slightly bluish red. 1 -I hydroxyethylamino 3methylbluish red bluish red.

enzene. l-amino-Z-ethoxynaphthalene bluish violet. 1 N hydroxyethylamino3 methyl; bluish red.

benzene.

benzene.

I claim: 1. Water insoluble monoazo dyestufis corresponding to theformula R Qatar-AFN wherein Ar stands for an aromatic radical selectedfrom the group consisting of the benzene and naphthalene series, saidradical bearing the azo bridge and the group in p-position to eachother, R stands for a member selected from the group consisting ofhydrogen, lower alkyl, hydroxy lower alkyl, lower alkylated hydroxylower alkyl and hydroxy lower alkyl being attached to Ar in o-positionto the group, R for a radical selected from the group consisting ofhydrogen and lower alkoyl, and wherein the ben zene nucleus, bearing theCN-group, is a member selected from the groups consisting ofchlorocyanophenyl, dicyano-phenyl and lower alkyl-dicyano-phenyl, saiddyestuffs being free from sulfonic and carboxylic acid groups.

2. Water insoluble monoazo dyestufis corresponding to the followingformula:

wherein Ar stands for an aromatic radical selected from the groupconsisting of the benzene and naphthalene series, said radical bearingthe azo bridge and the C HA-OH wherein Ar stands for an aromatic radicalselected from the group consisting of the benzene and naphthalene seriesbearing the azo bridge and the group in p-position to each other, and Rfor a radical selected from the group consisting of hydrogen and loweralkoyl, and wherein the benzene nucleus, bearing the CN-group, is amember selected from the groups consisting of chlorocyanophenyl,dicyano-phenyl and lower alkyl-dicyano-phenyl, said dyestulfs being freefrom sulfonic and carboxylic acid groups.

4. Water insoluble monoazo dyestufls corresponding to the formula:

O C CH wherein Ar stands for an aromatic radical selected from the groupconsisting of the benzene and naphthalene series bearing the azo bridgeand the mm-o-occn,

0Com

group in p-position to each other, and wherein the benzene nucleus,bearing the CN-group, is a member selected from the groups consisting ofchlorocyanophenyl,

dicyano-phenyl and lower alkyl-dicyano-phenyl, said dyestuifs being freefrom sulfonic and carboxylic acid groups.

5. The dyestuff corresponding to the formula:

Cl QrhrrQNn-cm-om-on 6. The dyestutf corresponding to the formula:

on, cn-orr 0 g no N n 7. The dyestufi corresponding to the formula:

cn,.cn, o.occn, OK

OCCH; CN CH3 CH:

References Cited in the file of this patent UNITED STATES PATENTS2,173,417 Huber Sept. 19, 1939 2,289,376 McNally et al July 14, 19422,384,734 Felix et al. Sept. 10, 1945 2,387,987 Felix et al. Oct. 30,1945

1. WATER INSOLUBLE MONOAZO DYESTUFFS CORRESPONDING TO THE FORMULA 